KR20160138176A - A polymer composition, an article thereof and a process for preparing the same - Google Patents

Abstract

Here,
a) from 42.5% to 94% by weight of a thermoplastic matrix resin;
b) from 1% to 7.5% by weight of a laser direct structured additive; And
c) 5% to 50% by weight of fiber reinforcement
A thermoplastic composition that can be activated after laser activation,
Said weight percent being based on the total weight of the composition;
Wherein the laser direct structured additive is a thermoplastic composition represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , wherein x is greater than 0.60 and less than 0.85.

Description

[0001] POLYMER COMPOSITION, PRODUCTS OF THE SAME, AND PROCESS FOR PRODUCING THE SAME [0002]

The present invention relates to a thermoplastic polymer composition comprising a laser direct structuring (LDS) additive. In particular, the present invention relates to a product made by the LDS method and a method of making the same.

Laser direct structuring (LDS) is a method that can form a separate conductive circuit path by selectively plating metal and injection molded products. First, plastic articles are injection molded using polymeric compounds specifically formulated for this process. The article is then activated with a laser of the desired pattern, thereby activating the surface of the article at the portion described using the laser. The article is then subjected to an electroless plating process with a metal such as copper, nickel, or gold, and the resulting circuit path exactly matches the lator pattern.

The advantage of the Laser Direct Structured (LDS) method is the ability to apply the actual 3D circuit path by having circuit paths along the contours of the injection molded article. By integrating the circuit directly onto the plastic article, the designer now has the freedom that was previously unavailable. This freedom of design allows for consolidation, weight reduction, miniaturization, reduced assembly time, improved reliability and reduced overall system cost.

Key markets and applications for laser direct structured methods include medical, automotive, aerospace, military, radio frequency (RF) antennas, sensors, home security and connectors.

US 2009/0292051 (SABIC: SABIC) discloses a high dielectric constant thermoplastic composition that can be used in a laser direct structuring method. The composition comprises a thermoplastic base resin, a laser direct structured additive, and at least one ceramic filler. The thermoplastic composition can be plated after activation using a laser, including:

a) from 10 to 90% by weight of a thermoplastic base resin;

b) from 0.1 to 30% by weight of a laser direct structured additive; And

c) from 10 to 80% by weight of one or more ceramic fillers.

The composition provides a high dielectric constant, low loss tangent thermoplastic composition. Copper chromium oxide spinel is used as a direct structured additive.

US 2012/0279764 (SABIC) discloses thermoplastic compositions that can be used in laser direct structuring methods to provide enhanced plating performance and excellent mechanical properties. The composition of the patent includes a thermoplastic base resin, a laser direct structured additive and a white pigment.

The thermoplastic composition may comprise,

a) 65 to 92% by weight of a thermoplastic base resin;

b) from 0.5 to 20% by weight of a laser direct structured additive; And

c) from 0.5 to 15% by weight of one or more pigments selected from TiO ₂ comprising a combination comprising at least one of the following: anatase, rutile, uncoated ZnO, BaSO ₄ , CaCO ₃ , BaTiO ₃ ,

Lt; / RTI > and may be activated using a laser and then plated,

The laser direct structured additive may be a heavy metal mixture oxide spinel, such as copper chromium oxide spinel; Copper salts such as copper hydroxide, copper phosphate, copper sulfate, cuprous thiocyanate; Or a laser direct structured additive as described above.

US 2004/0241422 (LPKF) discloses a method of depositing a metal layer on an electrically nonconductive support material by depositing a metallized layer on the metal nuclei produced using electromagnetic radiation to decompose the electrically nonconductive metal compound dispersed in the support material A method of generating a conductive track, and a method of generating it, are disclosed. The electrically nonconductive metal compound is a high-grade oxide which is stable in heat, stable in an acidic or alkaline digesting bath, stable in heat and stable in an acidic or alkaline digesting bath, is an oxide having a spinel structure, Insoluble spinel-based inorganic oxide. The spinel-based inorganic oxide used is heat-resistant and remains stable after experiencing the soldering temperature. The conductor tracks are robust and easily produced and strongly attached to the support.

US 2008/0015320 (DU-PONT) discloses a process for the preparation of a polymer composition which comprises adding to the polymer composition a quantity of 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96 or 97% ≪ / RTI > The total weight of the polymer composition was determined to be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, %, Based on the total weight of the composition, of a spinel crystal filler, and a process for producing the same. In the examples of this document, CuCr ₂ O ₄ is used as the spinel.

In the prior art based on LPKF technology, CuCr ₂ O ₄ spinel is used as a laser direct structured additive which can use matrix resins used in laser direct structuring methods. One drawback of using a CuCr ₂ O ₄ spinel as the LDS additive is that the CuCr ₂ O ₄ spinel that harmful to the mechanical properties of the matrix polymer. Therefore, the application of the resulting polymer will be limited. On the other hand, it has been observed that spinel such as NiFe ₂ O ₄ can not be plated at all and is poor in mechanical properties. Herein, CuCr ₂ O ₄ is to give the thermoplastic polymer composition, which addition is replaced by the other additives, Ni-Zn ferrite (ZnFe ₂ O ₄ with NiFe ₂ O ₄ doped with) may be plated after being activated using a laser. Compared to compositions using CuCr ₂ O ₄ spinel as an LDS additive, the mechanical properties of the resulting compositions herein are improved.

Here,

a) from 42.5% to 94% by weight of a thermoplastic matrix resin;

b) from 1% to 7.5% by weight of a laser direct structured additive; And

c) 5% to 50% by weight of fiber reinforcement

≪ / RTI > and can be plated after being activated by a laser;

Said weight percent being based on the fill weight of the composition;

Wherein the laser direct structured additive is a thermoplastic polymer composition represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , where x is greater than 0.60 and less than 0.85.

The thermoplastic matrix resin may comprise one or more compounds selected from the group consisting of polyesters, polyamides, polyphenylene sulfides, polyphenylene oxides, polysulfones, polyarylates, polyetheretherketones, polyetherimides, and mixtures and / Can be selected.

Preferably, the thermoplastic matrix resin comprises a polyamide. Representative examples include, but are not limited to, homopolyamides such as polyamide 6, polyamide 66, polyamide 56, polyamide 46, polyamide 4T, polyamide 5T, polyamide 6T, polyamide 6I, polyamide 7T, polyamide 8T , Polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T, polyamide MXD6, and copolyamides thereof; More preferably, the thermoplastic matrix resin is a polyamide which melts at above 265 DEG C, such as polyamide 4T, polyamide 5T, polyamide 6T, polyamide 6I, polyamide 7T, polyamide 8T, polyamide 9T, polyamide 10T, Polyamide 11T, polyamide 12T, polyamide MXD6, and copolyamide and / or polyamide 4T thereof, polyamide 5T, polyamide 6T, polyamide 6I, polyamide 7T, polyamide 8T, polyamide 9T, 10T, polyamide 11T, polyamide 12T, or polyamide MXD6 copolymerized with at least one selected from polyamide 6, polyamide 66, polyamide 56 and polyamide 46; Polyamide 6T / 10T, polyamide 6T / 10T, polyamide 6 / 6T, polyamide 6 / 6T, polyamide 6 / 6T, polyamide 6 / 10T, polyamide 66 / 6T, polyamide 46 / 4T, Amide 66 / 4T / 46 [which is a copolyamide of polyamide 66, polyamide 4T and polyamide 46], polyamide 6T / 4T / 46 [which is a polyamide 6T, a polyamide 4T and a polyamide 46 copolyamide , Polyamide 6T / 66/46 [copolyamide of polyamide 6T, polyamide 66 and polyamide 46], polyamide 6T / 5T / 56 [polyamide 6T, polyamide 5T and copolyamide of polyamide 56 Amide] and polyamide 6T / 66/56 [copolyamide of polyamide 6T, polyamide 66 and polyamide 56]; Most preferably, the thermoplastic matrix resin is a polyamide 66 / 4T / 46, a polyamide 6T / 4T / 46, a polyamide 6T / 66/46, a polyamide 6T / 5T / 56 and a polyamide 6T / 66/56; Even more preferably, the thermoplastic matrix resin is a polyamide 66 / 4T / 46, such as Stanyl ForTii (trademark) DS100.

The amount of thermoplastic matrix resin present in the composition of the present invention is based on the selected properties of the composition as well as the shaped article made from such a composition. Factors include the type and / or amount of LDS additive used.

Preferably, the thermoplastic matrix resin is present in an amount of from 42.5 wt% to 94 wt%, more preferably from 50 wt% to 80 wt%, and most preferably from 65 wt% to 75 wt%.

The thermoplastic matrix resin may be reinforced by the addition of a fiber reinforcing agent. Any suitable fiber reinforcement, such as glass fiber, carbon fiber, basalt fiber or aramid fiber, may be used in the present invention. The fiber reinforcement is present in an amount of from 5% to 50% by weight, preferably from 15% to 35% by weight, more preferably from 20% to 30% by weight, most preferably about 30% by weight.

In addition to thermoplastic matrix resins, the compositions of the present invention also include laser direct structured (LDS) additives. The LDS additive is selected so that the composition can be used in the LDS method. In the LDS method, an LDS additive is placed on the surface of the composition and exposed to a laser beam to activate metal atoms from the LDS additive. As described above, the LDS additive is selected such that the metal atoms are activated when exposed to the laser beam and are not exposed to the metal atoms in the areas not exposed to the laser beam. In addition, the LDS additive is selected so that the etched region after being exposed to the laser beam can be plated to form a conductive path in accordance with a standard electroless plating process, such as a copper plating process. Other electroless plating processes that may be used include, but are not limited to, gold plating, nickel plating, silver plating, galvanizing, tin plating, and the like.

The purpose of using the LDS additive is to form a metal seed on the laser etched surface and the final metallization layer during the subsequent plating process.

Existing laser direct structured additives are represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , where x is greater than 0.60 and less than 0.85. Zn _X Ni _(1-x) Fe ₂ O ₄ is a kind of nickel-zinc ferrite having a spinel structure. This is not a simple mixture of ZnFe ₂ O ₄ and NiFe ₂ O ₄ . Also, This is described in some documents as NiFe ₂ O ₄ doped with ZnFe ₂ O ₄ . In connection with this application, Zn _X Ni _(1-x) Fe ₂ O ₄ can also be expressed as the molar ratio of Zn and Ni in the nickel-zinc ferrite. For example, Zn _{0 . 75} Ni _{0 . 25} Fe ₂ O ₄ can be represented by 75Zn / 25Ni. Zn Fe ₂ O ₄ can be represented by 100 Zn, and Ni Fe ₂ O ₄ can be represented by 100 Ni.

Preferably, the X value is greater than 0.65 and less than 0.80; More preferably greater than 0.70 and less than 0.75; Most preferably, the X value is 0.75 and the laser structuring additive is Zn _0.75 Ni _0.25 Fe ₂ O ₄ .

The amount of LDS additive included is sufficient to coat the conductive path formed after activation by the laser without adversely affecting the mechanical properties. In one example, the LDS additive is present in an amount of 1 wt% to 7.5 wt%, preferably 2.5 wt% to 6 wt%, more preferably 3 wt% to 5 wt%, and most preferably 5 wt% . In general, the greater the number of laser direct structured additives present, the better the resulting plating quality. When the amount of the laser structuring additive exceeds 7.5% by weight, the mechanical performance of the material will be disadvantageous.

The particle size dispersion of the laser structured additive is suitably 50 nm to 50 mu m, preferably 100 nm to 10 mu m, more preferably 0.5 mu m to 3 mu m.

Preferably, the thermoplastic composition comprises, based on the total weight of the composition

d) from 0 to 30% by weight of a flame retardant;

e) 0 to 20% by weight of other additives

.

Any of the flame retardants well known to those skilled in the art may be used in the present invention. Preferably, the flame retardant is selected from, but not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, nitrogen based flame retardants such as melamine and melamine derivatives, phosphorus flame retardants such as organic and inorganic phosphates, phosphonates, phosphinates , E.g., metal phosphinate, and acyl; A combination of a phosphorus-based flame retardant, a nitrogen-based flame retardant and a phosphorus-based flame retardant; More preferably a metal phosphinate.

The flame retardant may be modified by any method well known to those skilled in the art before the flame retardant is added to the composition.

The flame retardant of component d) is suitably present from 0% to 30% by weight, preferably from 10% to 30% by weight.

The additives of component e) can be added to any of the additives well known to those skilled in the art such as pigments, antioxidants, light stabilizers, heat stabilizers, antistatic agents, UV absorbers, release agents, lubricants, Other fillers may be suitable for improving other properties.

The additive of component e) suitably is present from 0% to 20% by weight, preferably from 0.5% to 5% by weight.

In addition,

A molded article having an activated pattern;

A copper layer plated on the activated pattern to form a conductive path

Lt; RTI ID = 0.0 > a < / RTI &

The molded article

a) from 42.5% to 94% by weight of a thermoplastic matrix resin;

b) from 1% to 7.5% by weight of a laser direct structured additive; And

c) 5% to 50% by weight of fiber reinforcement

≪ / RTI > is formed from a thermoplastic composition that can be plated after activation using a laser;

Said weight percent being based on the total weight of the composition;

The laser direct structured additive is represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , where x is greater than 0.60 and less than 0.85.

The articles disclosed herein may be used in the fields of medicine, automotive, aerospace, military, RF antennas, sensors, home security and connectors.

In addition,

Molding the article from the thermoplastic composition;

Forming an activated pattern on the shaped article using a laser; And

Plating a copper layer over the activated pattern to form a conductive path

The method comprising the steps of:

The thermoplastic composition may comprise, based on the total weight of the composition,

a) from 42.5% to 94% by weight of a thermoplastic matrix resin;

b) from 1% to 7.5% by weight of a laser direct structured additive; And

c) 5% to 50% by weight of fiber reinforcement

≪ / RTI > and may be activated using a laser and then plated;

The laser direct structured additive is represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , where x is greater than 0.60 and less than 0.85.

The thermoplastic compositions of the present invention can be formed using any known method of combining the multiple components to form a resin. In one embodiment, the components were first blended in a high-speed mixer or in another low shear process. The formulation was then fed through a hopper to the throat of a twin-screw extruder. The extruder generally operates at a temperature higher than the temperature required to cause the flow of the composition.

When the thermoplastic resin is used as a matrix resin, the LDS additive is synthesized in an extruder with a thermoplastic resin and / or other additives and / or a flame retardant to obtain a desired composition.

Articles made, formed or molded, such as compositions, are also provided. Thermoplastic compositions can be formed into useful molded articles by a variety of means such as injection molding, extrusion, rotary molding, blow molding, and thermoforming, for example housings for computers, notebooks and portable computers, housings for mobile phones and other such communication equipment; Medical applications, automotive applications, and the like.

Example

The present invention can be illustrated by the following examples, but is not limited thereto.

material

Polyamide: Stannyl Portey (trademark) DS100 from DSM.

LDS additive:

Shepherd Black 1G (CuCr ₂ O ₄ ), a product commercially available from the Shepherd Color Company,

Product series Neo F20FERPO [75Ni / 25Zn]: Neo F2FERPO [50Ni / 50Zn] commercially available from Neosid Pemetzrieder GmbH &Co; Neo MIX25Ni75Zn [25Ni / 75Zn]; Neo MIX100Zn [100Zn]; Neo F100 [100Ni].

Glass fiber: Standard glass short fibers from PPG Industries Inc. - CIPC 3014B.

Plating bath composition: Enplate (TM) chemical solution obtainable directly from Enthone GmbH.

Example 1

65 wt% Stanny Forti (TM) DS100, 30 wt% glass fibers, and 5 wt% additives were mixed with Kraus Maffei Berstorff according to standard DSM Stannol Forti (TM) Were mixed in a ZE25 twin-screw extruder. After extrusion, the obtained mixed material was cut into granules for injection molding. During the injection molding process, these granules formed plaques measuring 80 x 80 x 2 mm. The injection-molded plaques were then placed in a Trumph Laser Mark Machine with the following parameter settings shown in Table 1: The type of laser used is an Nd: YAG laser with a wavelength of 1064 nm.

The temperature of the plating bath was raised to 48 캜 and the temperature was maintained at 48 캜. After laser treatment, the laser treated plaques were thoroughly impregnated in a copper electroless plating bath for 30 minutes. Before and after plating, the plaques were washed with deionized water.

The parameter settings of the laser instrument used in Example 1 and the plated generation-thickness of the plated copper layer on the plagues are shown in Table 1.

Pulse frequency (kHz)
/ Laser power
(% Of 200 W) 60/70 60/80 60/90 80/70 80/80 80/90 100/70 100/80 100/90 LDS Additive 100Ni 0 0 0 0 0 0 0 0 0 75Ni / 25Zn 0.1 0.5 0.9 0.1 0.4 0.7 0.1 0.3 0.5 50Ni / 50Zn 0.6 1.6 1.8 0.5 1.4 1.6 0.4 One 1.4 25Ni / 75Zn 0.8 3.1 3.6 0.9 2.2 3.5 0.9 2 3.3 100Zn 0.4 1.5 1.5 0.4 1.2 1.5 0.4 0.8 1.4 Black 1G (CuCr ₂ O ₄ ) 2.8 6.1 6.4 2.3 5.2 5.8 2 3.8 5.1

conclusion

From Table 1 it can be seen that the composition according to the invention comprising 25Ni / 75Zn LDS additive can be plated within 30 minutes and the resulting copper layer thickness is less than the thickness of the composition comprising (CuCr ₂ O ₄ ) Lt; RTI ID = 0.0 > 75Ni / 25Zn, 50Ni / 50Zn and 100Zn. ≪ / RTI >

Example 2

Mechanical properties

Granules containing 65% by weight of Stannyl Porty (TM) DS100, 30% by weight of glass fibers and 5% by weight of LDS additives were injection molded into standard bars for tensile test ISO 527 and Charpy test ISO 179, Are shown in Table 2 below.

E-modulus The tensile strength Elongation at break Charpy Bianchi Charpinot Mpa Mpa % kJ / M2 kJ / M2 [100Zn] 11138 126.5 1.26 30.78 3.75 [25Ni / 75Zn] 11240 124.9 1.24 29.34 3.65 [50Ni / 50Zn] 11393 106.2 1.04 29.11 3.33 [75Ni / 25Zn] 11444 110.3 1.08 29.06 3.56 [100Ni] 11226 106.3 1.07 26.91 3.04 Black 1G (CuCr ₂ O ₄ ) 11220 110.6 1.08 26.32 3.41

conclusion

According to the data shown in Table 2 above, comparing compositions comprising CuCr ₂ O ₄ with other compositions comprising Ni and / or Zn ferrite, the mechanical properties of compositions comprising 25Ni / 75Zn, ie, elongation at break and strength Was improved.

Claims (14)

(a) from 42.5% to 94% by weight of a thermoplastic matrix resin;
(b) 1% to 7.5% by weight of a laser direct structured additive; And
(c) 5% to 50% by weight of fiber reinforcement
A thermoplastic composition that can be activated after laser activation,
Said weight percent being based on the total weight of the composition;
Wherein the laser direct structured additive is represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , where x is greater than 0.60 and less than 0.85. The method according to claim 1,
x is from 0.65 to 0.80. 3. The method of claim 2,
x is 0.70 to 0.75, preferably 0.75; Wherein the laser direct structured additive is present in an amount of 2.5 wt% to 6 wt%, preferably 3 wt% to 5 wt%, more preferably 5 wt%. 4. The method according to any one of claims 1 to 3,
Wherein the reinforcing agent is at least one selected from glass fibers, carbon fibers, basalt fibers and aramid fibers, and is preferably glass fiber. 5. The method according to any one of claims 1 to 4,
Wherein the fiber reinforcing agent is present in an amount of from 10 wt% to 50 wt%, preferably from 15 wt% to 35 wt%, more preferably from 20 wt% to 30 wt%. 6. The method according to any one of claims 1 to 5,
Wherein the thermoplastic resin is at least one selected from the group consisting of polyesters, polyamides, polyphenylene sulfides, polyphenylene oxides, polysulfones, polyarylates, polyetheretherketones and polyetherimides, and mixtures and / or copolymers thereof Lt; / RTI > 7. The method according to any one of claims 1 to 6,
Wherein the thermoplastic matrix resin comprises a polyamide. 8. The method according to any one of claims 1 to 7,
Wherein the thermoplastic composition comprises at least one flame retardant selected from the group consisting of metal hydroxides, nitrogen-based flame retardants, and phosphorus flame retardants. 9. The method according to any one of claims 1 to 8,
Based on the total weight of the composition,
(d) 0 to 30% by weight of a flame retardant; And / or
(e) 0 to 20% by weight of other additives
≪ / RTI > 10. The method of claim 9,
Wherein the flame retardant is selected from the group consisting of metal hydroxides, nitrogen flame retardants and phosphorus flame retardants. A molded article having an activated pattern;
The copper layer plated on the activated pattern to form a conductive path
≪ / RTI >
The molded article
(a) from 42.5% to 94% by weight of a thermoplastic matrix resin;
(b) 1% to 7.5% by weight of a laser direct structured additive; And
(c) 5% to 50% by weight of fiber reinforcement
≪ / RTI > is formed from a thermoplastic composition that can be plated after activation using a laser;
Said weight percent being based on the total weight of the composition;
Wherein the laser direct structured additive is represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , where x is greater than 0.60 and less than 0.85. 12. The method of claim 11,
Wherein the thermoplastic composition is a composition as defined in any one of claims 1 to 10. Molding the article from the thermoplastic composition;
Forming an activated pattern on the shaped article using a laser; And
Plating the copper layer on the activated pattern to form a conductive path
1. A method of forming a product comprising:
The thermoplastic composition may comprise, based on the total weight of the composition,
a) from 42.5% to 94% by weight of a matrix resin;
b) from 1% to 7.5% by weight of a laser direct structured additive; And
c) 5% to 50% by weight of fiber reinforcement
Lt; / RTI > and may be activated using a laser and then plated,
Wherein the laser direct structured additive is represented by the formula Zn _x Ni _(1-x) Fe ₂ O ₄ , wherein x is greater than 0.60 and less than 0.85. 12. The method of claim 11,
Wherein the thermoplastic composition is a composition as defined in any one of claims 1 to 10.